Directed isomer formation in the oxo reaction



A ril 30, 1957 H. J. HAGEMEYER, JR.. ETAL 0,

DIRECTED ISOMER FORMATION IN THE OX0 REACTION Filed March 29 1954 m 0 5lO B 4 o 3 0 0/0 2 m QHQbQQtQ a??? kzwuvmi/ o u 5 m U R N .IO U u 2 R HBIO 3 N h %\w M 0 R 5 IQ 6 PERCENT ADDED ALDEHYDE /N TD7Z4L ALDEHYDEPRODUCT Hugh Jflageme e1; Jr: David a Hill I N V EN TORS' B Y I 5 A:ORNEYJ" United States Patentc) DIREGTED ISOMER FORMATION X0 I REACTIONHugh J 'HagemeyerQjJL; and David 'Ci 7 Hull; Longview,

'Tex.;- assignors to Eastman" Kodak- Company," Rochester; N. 'Y.,a-"corporationof New Jei-sey Application March.29,f1954; SeriaL-No;419,145

5 Glaims. (Cl. 260- 604) This application is a continuation-in-part ofourearlier applications"SerialNo. 22, 7 16; filedApril 22; 1948; nowPatent No.' 2,694,734, issued' Novemb-er' 16, 1954"and Serial Nof131;499,' filed December 611949 (a continuati'on-in part ofsaid-"Serial'No. 22,716 and of our now abandoned application SerialNo.78,938, filed March 1,

concerned with the reaction of nan olefin-With carbon monoxide andhydrogen inthe presence of one of thealdehyde isorners. form:ed as aproduct of the reaction-in order to suppressfurther formation of-thatisomer. It is -further.;specifically concernedwiththe reaction of 1ethylene with carbon monoxide and hydrogen iunder conditions suchthatthe formation of .diethyl ketoneis suppressed...- It/is furtherconcerned with a process for-reacting olefins including propylene and-'higher@ol'efins in the ypresence' of asuitable acetal and waterwhereby the formation of one or the other of the possible isomericaldehydes is suppressed. The inventi'onis'generally concerned a withmethods of controlling the-ratio of normal to. isoaldei hyde forme'dwinthe oxonation ofolefins. It'i'ssspecifically concerned with processeswherein the oxonation otolefins is carried I out. in the 4 presence Iof. particular aldehydes, .acetals, and/orketones zand aloohols.Theobjects of the invention-are directed tothese reactions.

Prior art methods andsolvents :usedfor carrying out the reaction ofcarbon monoxide and hydrogen witholefins and olefinic compounds resultin the formation of both normal and isoaldehydes-and usually in theratio .of 1:1 to. 1.5 :1. a The oxonationof-the-Jower aliphaticlolefins, ethylene and propylene, also-results in the formation ofsubstantial quantities of diethyl ketone and the mixed dipropylketones,- respectively. During our study of .theoxoprocess we havediscovered several new and -unpredictable methods of operationWhichcan-be used to control the ratiot of normal to isoaldehydeproduced,-and

= also to suppress the formationof ketones.

7 In normal operation the reaction of ethylene or propylone withcarbonmonoxide and. .hydrogen 'canberepre- Lsented byLthe followingequation:

where R. is..hydrogen, Ialliyl or aryl.

The ketones formed according .to Reaction 2 arepresent in amounts ;up ito- 30%. of the weight of-theproduct wise operationthe furtherformation. of the ketone can -=be suppressed.

Y In continu ous' operation me -formation "ofketone -is somewhat-lessandusually in the r ange of 5 and the fu'rther'formation of keto'neis oompletely suppressed by maintaining this concentration of keto'neinthe medium in the reactor-space.

The'oxoiiation of olefinsgi-ncluding propylene and above with a source'ofca'rbon monoxide and hydrogen results in the formation of a mixtureof normal'and isoalde'hydes aecrding to the equations:

Strai'ght chain or norrnalaldehyde information:

If the reactionis carried out in the presence bra astasndardcobalt-thoria-magnesia catalyst suspended-min others, alcohols, andhydrocarbons, or in the presence of soluble oobalt-oatalysts-such assolutions of cobalt carbonyl .in butanol, toluene, diethyl ether, or.the olefin itself, a 50:50 plus or minus 10 mixture .of. normal andisoaldehydes. is recovered. We' havenow discoveredan unusual-and novel:method by which it. is possible to direct the isomer-formationtofavoreither straight chain or. normal butyraldehyde formationto the exclusionof :theflalpha methyl or isoaldehyde formation, or viceversa. In fact,it ispossible .to operate underzoonditions disclosed -ai-rd disooveredby.us so that one or the other 'of the aldehyde isomers'canbe suppressedcompletely.

T We have ldisoovered-four methodsv of .oper'ation :by w'hi h weoan"direct the, isomer vformation in the 0x0 process.

- In the. first method of directing isomer formations in the ox-oprocess, we havefound' that by recycling one of "the .isomericaldehydeproducts, the further-formation of that particular isomer can besuppressed, and by operating in the pnes'enceof a large excess ofthatis'omenthe'further formation of the isomer can be eliminatedentirely.

Still another application of this-particular method is the suppressioniofvthe furtherv formation of .diethyl ketone and dipropyl ketone in theoxona-ti'onof ethylene .and

, propylene by recycling a substantial portion of that-ketone to thereactorgspace.

"The second method Fof directing isomer formation-in the oxo reactionisto carry. out the excitation ofsthe lolefin in the presence ofan. acetalof that isomer which it-isdesirked to suppress or eliininatef Inaddition to-the acetal the reactor. spacetusually containsv 110% w ater,and under these conditions the acetal exists in equilibrium with thefree aldehyde. Theequilibrium concentration of free aldehyde functionsasin- Method 1 to suppress further formation of that particular isomer.

"The third method of directing isomer formation-in the oxo reactiontakes advantage of the difference inlthe rate of acetal formation ofnormal and isoaldehydes. This is done 'by operating in a solventcomposed-predominantly of a primary or s'ecoiidarya'lcoh ol and underthese conditions the rate of formation of the acetal of the normalisomer to that of'ther isoaldehyde is approximately 5-10 times greater.For example, the reaction of normal butyraldehyde'wi-th butylalcohol toform dibutyl butal :is 10 times faster than the reaction ofisobutyraldehyde withtnorm al butyl alcohol to form dibutyl :isobutal.This in efiect maintains reaction conditions whereinan excess of theis'oaldehyde is present and thus the formation of the normal isomerpredominates. By maintaining ahigh 3. cation Serial No. 22,716 whereinthe reaction of an olefin with carbon monoxide and hydrogen is carriedout in the presence of a lower aliphatic ketone. This is acompletely'unexpected result and although we can 'ofier no explanationof why the ketone exerts such an effect on the oxo reaction, we havefound that the formation of the normal isomer predominates.

Although metallo-hydrocarbons and ketones are known to favor abnormaladditions in certain reactions, that is the formation of normalcompounds, we are aware of no prior art relating to the use ofaldehydes, acetals, alcohols, and/or ketones as a method of directingisomer formation in the oxo process. that the novelty in this processresides in the method and the concentration of aldehydes, acetals,alcohols, and/or ketones maintained in the reactor space rather than thesimple fact of carrying out the oxo reaction in the presence of asolvent selected from one of these classes. Thus, although it is truethat acetals and alcohols have previously been mentioned as componentsin oxo solvents, no one has ever deliberately used these solventsaccording to the method of our invention in order to control and/ordirect isomer formation in the oxo process.

In the process of the present invention an olefin or an olefiniccompound and a source of carbon monoxide and hydrogen are reacted in thepresence of a solution and/or suspension of a suitable cobalt catalystor mixed cobalt-iron catalyst. The reaction is carried out attemperatures ranging from 75-200 0., usually in the range of l30-l75 C.,and at 40700 atmospheres. Typical catalysts which may be used include areduced cobalt catalyst composed of 2545% cobalt, 2% thoria, 2%

magnesia, and the remainder kieselguhr, and 40-70% reduced or othersimilar solid catalysts suspended in the desired reactor composition. Wehave further found that the same results may be obtained when thereaction is carried out in the presence of a solution of cobaltcarbony]. The actual mechanics of the present invention are perhaps bestillustrated by the following examples, with regard to the first of whichwe have attached a drawing showing a plot of added aldehyde type andconcentration against percent n-butyraldehyde in the product.

2 EXAMPLE 1 A series of runs was made wherein propylene was reacted withcarbon monoxide and hydrogen in the presence of iso or normalbutyraldehyde and 20 g. of a 36% It must be remembered For purposes ofconvenience these results are also plotted in Figure 1. It isinteresting to note that the relationship between the percent addedaldehyde and the total aldehyde produced and the percent normalbutyraldehyde produced is almost a straight line relationship.

EXAMPLE 2 One hundred grams of the aldol trimer formed by the aldolcondensation of isobutyraldehyde, 10 g. of water, 20 g. reduced oxocatalyst described in Example 1, and 190 g. of normal butyl alcohol werecharged to a 1-liter stainless steel rocking autoclave. Two gram molesof propylene were reacted with an equimole mixture of carbon monoxideand hydrogen at 130-138" C. and at pressures ranging from 2,100-3,000 p.s. i. The reaction rate was 19.4 gram moles per hour and the aldehydeproduced by the oxo reaction was all normal butyraldehyde.

The aldol condensation was carried out as follows: 216 grams ofisobutyraldehyde and 20 grams of 28% sodium hydroxide were fed to acontinuous aldol reactor over a 2 hour period. The reaction temperaturewas held at 5-10 C. by cooling as required. The product was neutralizedwith acetic acid to pH=6, decanted, washed with water, decanted anddistilled at reduced pressure. One hundred ninety-two grams of theisobutyraldehyde hemiacetal of isobutyraldol were obtained.

Fifty grams of paraisobutyraldehyde, 2 g. of water, 20 g. of reduced oxocatalyst as described in Example 1, and 190 g. of normal butyl alcoholwere charged to a 1-liter stainless steel autoclave. Two gram moles ofpropylene were reacted at l30-l45 C. with pressures ranging from2,000-3,000 p. s. i. A reaction rate of 19.0 g. moles per hour wasobserved. Azeotropic distillation of the aldehydes from a 1% solution ofsulfuric acid in water showed that 85% of the aldehydes produced werenormal or the ratio of normal to isobutyraldehyde produced was 5.7: 1.

Examples 2 and 3 show that sources of isobutyraldehyde other thanmonomeric isobutyraldehyde produce the cobalt, 2% thoria, 2% magnesia onkieselguhr catalyst,

62% reduced and suspended in 190 g. of nolmal butyl alcohol, 10 g.water. All the runs were carried out at 2,0003,000 p. s. i. and attemperatures ranging from l30-l50 C. The reaction rates varied from 20.3to

32.8 grant moles per liter of reaction space per hour. Two gram moles ofpropylene were reacted in each run and at the end of the run theautoclave was emptied, the crude product filtered and distilled from anequal volume of 1% sulfuric acid solution. The iso and normalbutyraldehydes were recovered as the azeotropes. The results 1 aretabulated in Table I which reports the percent added aldehyde in thetotal aldehyde product and also the percent normal butyraldehydeproduced.

Table I iso-H1311 same results. Apparently the aldol trimer and the paraaldehyde trimer break down under oxo condition. The use of the trimersis particularly valuable in continuous operation since a high throughputand high rate of reaction for a given reactor space make it desirable tokeep the partial pressures due to the reactor liquid compositions as lowas possible.

EXAMPLE 4 Two hundred grams of normal propyl alcohol, 10 g.

' of water, and 20 g. of reduced oxo catalyst as described in Example 1were charged to a l-liter stainless steel autoclave. Ethylene wasreacted with carbon monoxide and hydrogen at l40-153 C. and at2,300-3,200 p. s. i. After two gram moles of ethylene had beenreacted,the crude reaction product was filtered and charged to a still with anequal volume of 1% of sulfuric acid and water. Distillation gave 24 g.of propionaldehyde, 7.5 g. of diethyl ketone and 3 g. of propyl alcohol.

In a second run employing 190 g. of propyl alcohol, 10 g. of diethylketone, 10 g. of water, and 20 g. of reduced oxo catalyst, two grammoles of ethylene were oxonated at -l48 C. and at pressures ranging from2100-3000 p. s. i. The crude reaction product was filtered and chargedto a still with an equal volume of 1% sulfuric acid and water.Distillation gave 77 g. of propionaldehyde,9.6 g. of diethyl ketone.Acomparison of the two runs shows that by incorporating a small amountof diethyl ketone in the initial charge to the autoclave the furtherformation of this ketone was completely suppressed.

EXAMPLE A continuous oxo reactor 9" inner diameter and 20 high wascharged with 30 gallons of propyl alcohol containing weight percent of acobalt-thoria-magnesia oxo catalyst 60% reduced. Ethylene, carbonmonoxide, and hydrogen were fed continuously through the reactor andunreacted gases were continually cycled through the reactor by acompressor. The ethylene concentration in the reactor space wasmaintained between 10-18%, the carbon monoxide concentration between20-35% with the residual gas being hydrogen and a small amount ofinerts. During one period of operation a total of 16,890 pounds ofpropionaldehyde was produced with an over all yieldfrom ethylene of75.2%. In this operation the propionaldehyde was distilled out as formedtogether with substantial amounts of the azeotropes of diethyl ketone,propanol, and dipropyl propional. The crude product from the reactor wasstripped of propionaldehyde, and the residual material including diethylketone, ethyl a1- cohol, and dipropyl p-ropional was recycled to thereactor continuously. In this same period the total yield or productionof diethyl ketone was only 290 pounds. It can be assumed that most ofthe diethyl ketone was produced in the. first several days of operation.

In a second period of operation a total of 13,277 pounds ofpropionaldehyde was produced with an over-all yield from ethylene of77%. During this same period, in which the diethyl ketone produced inthe previous period was continuously recycled to the reactor, there wasno increase in the inventory of diethyl ketone.

The above examples show that both in the batchwise and continuousoxonation of ethylene the formation of diethyl ketone can be completelysuppressed by maintaining a concentration of this ketone in the reactorspace. ture, pressure, catalyst activity andreactor liquid composition.Under the oxonation conditions used in the above runs, a diethyl ketoneconcentration of 5-10 percent in the reactor space is sufficient.

EXAMPLE 6 Runs 1-4. (below) show the effect of using the butals ofnoramal butyraldehyde and isobutyraldehyde on the formation of aldehydeisomers in the oxonation of propylene. In each run two gram moles ofpropylene were oxonated at temperatures ranging from 130-155 C. andpressures of 2100-3000 p. s. i. The reaction rates averaged 13.8-22.4gram moles per hour per liter of reactor space. In each run 190 g. of abutal, 10 g. of water, and 20 g. of reduced oxo catalyst were charged toan autoclave of l-liter capacity. Run 3 was a check run employing butylalcohol as the solvent. These runs are summarized in Table II.

Table 11 Percent Ratio n- Run Medium n-HBu to iso- Produced HBu Dibutyllsobutal 93 13. 3/1 Dibutyl n-butal 56.5 1.3/1 Butanol 66. 6 2/1 D utylisobutal 85.5 6.2/1

The concentration required varies with tempera- EXAMPLE 7 In thecontinuous production of butyraldehydes a reactor 20 high and 9" innerdiameter and containing 3 0 alternating partial plates was charged witha slurry of 30 pounds of solid catalyst with a composition of 38%cobalt, 2% thoria, 2% magnesia, 58% Supercel, and 64% reduced in 20gallons of butyl alcohol. The catalyst slurry was heated to by cycling afeed gas rich in hydrogen through a preheater and then through thecatalyst slurry in the reactor. Propylene was pumped in gradually to therecycle gas stream immediately before the preheater and the exothermicreaction was allowed to bring the temperature in the reactor to -170 C.This temperature was maintained by controlling the temperature of theincoming recycle gas and by distilling out the aldehyde as formed.Although the reaction was started with pure butyl alcohol containing 3-5water, there was a wide variation in the reactor liquid composition dueto the formation of high boilers. The high boilers are comprised mainlyof butals. In continuous operation a crude product containing from15-45% butyraldehydes is distilled off continuously, depressurized, andpumped to a distillation system. After stripping out the aldehydeazeotropes, the remainder is recycled to the reactor to maintain areactor level. Operating in this manner the only butyl alcohol fed tothe reactor is that used to slurry make-up catalyst. As a result thereactor liquid composition is generally comprised of 5-10% butylalcohol, 75-80% mixed butals, and 10-15% unidentified high-boilers. Therate of production of this unit was stabilized at 1200-1500 pounds perday of mixed butyraldehydes and the ratio of normal to isobutyraldehydeaveraged -1.65:l. This operation is discussed in greater detail in ourapplication Serial No. 318,888, filed November 5, 1952, as acontinuation-in-part of the above-mentioned application Serial No.78,938, said application Serial No. 318,888 having issued as Patent No.2,748,167 on May 29, 1956.

In an alternate method of operation the crude product distilled from thereactor is depressurized, and pumped to a distillation system, strippedof the butyraldehyde azeotropes, and a portion of the residual reactorliquid is led to a hydrolysis column containing 1% sulfuric acid inwater wherein the butals are hydrolyzed to recover butyraldehydes andbutyl alcohol. In this manner the butyl alcohol content of the reactorliquid can be increased by feeding butyl alcohol as well as butals formake-up liquid. We found that the ratio of normal to isobutyraldehydeproduced varied directly with the percent butyl alcohol maintained inthe reactor liquid. The results for several periods of operation whereinsubstantial quantities of mixed aldehydes were produced whilemaintaining set limits of butyl alcohol concentration in the reactorspace are. listed in Table III.

In a continuous reaction it is necessary to operate with a substantialquantity of recycle gas in order to remove the heat of reaction. Thisrecycle gas strips the reactor of monomeric aldehyde so that thealdehyde concentration of the reactor seldom exceeds 1 to 2%. However,it can be seen from Table III that even at these low aldehydeconcentrations, the preferential removal of one of isomers has aprofound effect on the ratio of isomers formed.

Additional evidence for the effect of butal formation on the ratio ofisomers formed is presented in the foliowing examples run batchwise. 'InExample 8 which follows, the rate of reaction was 11.4 gram moles perliter of reaction space per hour and the ratio of normal toisobutyraldehyde formed was 26:1. in Example 9 the rate of reaction was33.2 gram moles per liter of reaction space per hour and the ratio ofnormal to isobutyraldehyde formed was 1.8:1. From this data it can beseen that, if there is sutficient time for the butal formation, thegreatest effect due to butal formation is realized.

EXAMPLE 8 One hundred and ninety grams butanol, 10 g. of water, and 20g. of reduced oxo catalyst were charged to a l-liter stainless steelautoclave and 2 gram moles of propylene were oxonated with carbonmonoxide and hydrogen at 140-165" C. and 2,3003,200 p. s. i. The rate ofaldehyde production in this run was 11.4 gram moles per liter ofreaction space per hour.. The crude product was filtered and togetherwith an equal volume of 1% sulfuric acid charged to a distillationcolumn. Azeotropic distillation of the butyraldehydes gave a ratio ofnormal to isobutyraldehyde of 2.6: 1.

EXAMPLE 9 In a second run employing the same charge as Exampie 8 plus apreactivation period wherein the catalyst was treated with carbonmonoxide and hydrogen at 90 C. and 2500 p. s. i. for 30 minutes, therate of butyraldehyde formation was 33.2 gram moles per liter ofreaction space per hour. Distillation of the aldehyde formed gave anormal to isobutyraldehyde ratio of 1.8:1.

Still another method of directing isomer formation in the oxo process isto employ a lower aliphatic ketone as a solvent or reaction medium. Theetfect of a ketone solvent is shown in Example 10.

EXAMPLE 10 Eight grams of cobalt carbonyl dimer were dissolved in 200 g.of methyl ethyl ketonee. The solution was charged to a l-liter autoclaveand 2 gram moles of butylene together with excess carbon monoxide andhydrogen were charged to the autoclave at 2,200-3,500 p. s. i. and140-163 C. The reaction was complete in 16 minutes and the contents ofthe autoclave were blown off and condensed. The crude product, togetherwith an equal volume of 1% sulfuric acid, was charged to a distillationcolumn and fractionation gave 23 g. of isovaleraldehyde and 131 g. ofnormal valeraldehyde, or a ratio of normal valeraldehyde toisovaleraldehyde of. 5.7: 1.

From the above examples it can be seen that the invention is generallyconcerned with methods of operation wherein the ratio of normal toisoaldehyde formed in the oxonation of olefins can be controlled. It isspecifically concerned with processes wherein the oxonation of olefinsand olefinic compounds is carried out in the presence of optimumconcentrations of aldehydes, acetals,

alcohols, and/or ketones. These examples are merely illustrative of theinvention and are not to be interpreted in a limiting sense.

We claim: H I

1. The process of producing organic carbonyl compounds wherein theformation of isomers is directed by carrying out the reaction of anolefin or olefinic compound with carbon monoxide and hydrogen, in thepresence of a catalyst selected from cobalt and iron in a form capableof catalyzing the oxo reaction, at temperatures ranging between about 40and 200 C. and at a pressure between about 40 and 700 atmosphereswherein the reaction is carried out in the presence of a substantialadded quantity of one of the isomeric aldehydes produced in thereaction, thereby directing the reaction to the formation of the otheraldehyde isomer.

2. The process of claim 1 in which the source of isomeric aldehydes isselected from dimers and trimers of the aldehydes.

3. The process of producing organic carbonyl compounds which comprisesreacting with carbon monoxide and oxygen in the. presence of a catalystselected from cobalt and iron in a form capable of catalyzing the oxoreaction, at a temperature ranging between 40-200 C. and at a pressureranging from 40-700 atmospheres on an organic substance selected fromthe group which consists of aliphatic and cyclic olefins to produce amixture of normal and isoaldehydes wherein the reaction is carried outin a solvent medium comprised of an added quantity of acetal of one ofthe isomeric aldheydes, thereby directing the reaction to the formationof the other isomeric aldehyde.

4. The process for producing butyraldehydes by reacting propylene withcarbon monoxide and hydrogen in. the presence of a catalyst selectedfrom cobalt and iron in a form capable of catalyzing the oxo reaction,at a temperature ranging between 40-200 C. and at a pressure rangingbetween 40-700 atmospheres, wherein the reaction is carried out'in thepresence of an acetal of isobutyraldehyde, which in turn is a source ofisobutyraldehyde via a replacement reaction with normal butyraldehydeand thus represses further formation of isobutyraldehyde.

5. The process for producing aldehydes by reacting an aliphatic olefinichydrocarbon with carbon monoxide and hydrogen in the presence of acatalyst selected from cobalt and iron in a form capable of catalyzingthe oxo reaction, at a temperature ranging between 40-200 C. and at apressure ranging between 40-700 atmospheres to produce a mixture ofnormal and isoaldehydes, wherein the reaction is carried out in thepresence of an acetal of one of the isomeric aldehydes, therebydirecting the reaction to the formation of the other isomeric aldehyde.

References Cited in the file of this patent UNITED STATES PATENTS2,509,878 Owen May 30, 1950 ,7 2,530,989 Parker Nov. 21, 1950 2,535,069Johnson Dec. 26, 1950 2,694,734 Hagemeyer et al Nov. 16, 1954 2,694,735Hull et al. Nov. 16, 1954

1. THE PROCESS OF PRODUCING ORGANIC CARBONYL COMPOUNDS WHEREIN THEFORMATION OF ISOMERS IS DIRECTED BY CARRYING OUT THE REACTION OF ANOLEFIN OR OLEFINIC COMPOUND WITH CARBON MONOXIDE AND HYDROGEN, IN THEPRESENCE OF A CATALYST SELECTED FROM COBALT AND IRON IN A FORM CAPABLEOF CATALYZING THE OXO REACTION, AT TEMPERATURES RANGING BETWEEN ABOUT40* AND 200*C. AND AT A PRESSURE BETWEEN ABOUT 40 AND 700 ATMOSPHERESWHEREIN THE REACTION IS CARRIED OUT IN THE PRESENCE OF A SUBSTANTIALADDED QUANTITY OF ONE OF THE ISOMERIC ALDEHYDES PRODUCED IN THEREACTION, THEREBY DIRECTING THE REACTION TO THE FORMATION OF THE OTHERALDEHYDE ISOMER.